The Chemistry of Dianion‐Type Zinc Ate Complexes
The Chemistry of Dianion‐Type Zinc Ate Complexes
复制标题
双阴离子型锌配合物的化学性质
DOI：
10.1002/chin.200714232
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
Y. Kondo
中科院分区：
文献类型：
--
作者：
M. Uchiyama;Y. Kondo
用于化学、区域和立体选择性地将各种官能团引入有机分子的工具的适用性仍然相当有限。描述了我们通过开发二阴离子型锌配合物化学来功能化有机化合物的新方法。四配位双阴离子型锌酸盐的反应性和选择性长期以来一直被忽视。芳香环上的卤素-锌交换反应以及使用二价阴离子型锌酸盐对末端炔烃（和烯烃）进行甲硅烷基锌化，然后进行亲电捕获，被证明是形成 C-C 键的有力工具。还发现官能化的芳香族或脂肪族锌酸盐中间体可以进行铜和钯催化的 C-C 键形成反应，具有良好的产率和高化学选择性。另一方面，一价阴离子型和二价阴离子型锌酸盐之间的环氧化物开环反应的区域选择性存在显着差异。这些结果清楚地表明，这些二价阴离子型锌酸盐在结构、反应性和选择性方面应与普通三配位一价阴离子型锌酸盐区别开来，因此它们将为有机合成化学打开一扇新的窗口。
Tools for chemo-, regioand stereo-selective introduction of various functional groups onto organic molecules are still quite limited in their applicability. Our new approaches to functionalizing organic compounds by means of development of the chemistry of dianion-type zinc ate complexes are described. Reactivity and selectivity of tetra-coordinated dianion-type zincates have been ignored for a long time. Halogen-zinc exchange reaction on aromatic rings and silylzincation of terminal alkynes (and alkenes) using dianion-type zincates followed by electrophilic trapping proved a powerful tool for C-C bond formations. The functionalized aromatic or aliphatic zincate intermediate was also found to undergo copperand palladium-catalyzed C-C bond-forming reactions with good yields and high chemoselectivity. On the other hand, a sharp difference in regioselectivity in the epoxide-opening reaction between monoanion-type and dianion-type zincates was disclosed. These results clearly suggest that these dianion-type zincates should be distinguished from ordinary tri-coordinated monoanion-type zincates in terms of structure, reactivity, and selectivity, and hence they would open a new window in synthetic organic chemistry.